Oxidation and thermal degradation of methyldithanolamine/piperazine in CO₂ capture

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Abstract

The solvent 7 molal (m) methyldiethanolamine (MDEA)/2 m piperazine (PZ) presents an attractive option to industry standard solvents including monoethanolamine (MEA) for carbon dioxide (CO₂) capture in coal-fired power plant flue gas scrubbing applications. The solvent was tested under thermal and oxidizing conditions, including temperature cycling in the Integrated Solvent Degradation Apparatus (ISDA), to measure rates of degradation for comparison to other solvents. Unloaded 7 m MDEA/2 m PZ was generally thermally stable up to 150 °C, exhibiting very low loss rates. However, at a loading of 0.25 mol CO2/mol alkalinity, loss rates of 0.17 ± 0.21 and 0.24 ± 0.06 mM/hr, respectively, for MDEA and PZ were measured. No amine loss was observed in the unloaded blend. Thermal degradation was modeled as first-order in [MDEAH⁺], and a universal Ea for amine loss was estimated at 104 kJ/mol. An oxidative degradation model for 7 m MDEA was developed based on the ISDA data. From the model, the rate of amine loss in 7 m MDEA/2 m PZ was estimated at 1.3 X 10⁵ kg/yr, based on a 500 MW power plant and 90% CO₂ capture. In terms of amine loss, the solvent can be ranked with other cycled solvents from greatest to least as follows: 7 m MDEA>7 m MDEA/2 m PZ>8 m PZ. Thermal degradation pathways and mechanisms for 7 m MDEA/2 m PZ include SN2 substitution reactions to form diethanolamine (DEA), methylaminoethanol (MAE), 1-methylpiperazine (1-MPZ), and 1,4-dimethylpiperazine (1,4-DMPZ). The formation of the amino acids bicine and hydroxyethyl sarcosine (HES) has been directly tied to the formation of DEA and MAE, respectively, through oxidation. As a result of the construction and operation of the ISDA for cycling of solvents from an oxidative reactor to a thermal reactor, several practical findings related to solvent degradation were made. The ISDA results demonstrated that increasing dissolved oxygen in solvents leaving the absorber will increase the rate of oxidation. A simple N2 gas stripping method was tested and resulted in a reduction to 1/5th the high temperature oxidation rate associated with dissolved oxygen present in the higher temperature regions of an absorber/stripper system. The ISDA experiments also demonstrated the need to minimize entrained gas bubbles in absorber/stripper systems to control oxidation. When the ISDA was modified to intercept entrained gas bubbles, the oxidation rate was reduced 2 to 3X.